Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
  • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]

Definitions

• the invention relates to glass-ceramics whose
• Optimization lies in the change in the composition of the starting glasses or in the variation of the heating rate, which can be driven faster or slower.
• composition for example, lower processing temperatures are sought.
• the composition also has an influence on the
• a challenge in the production of glass ceramic is the production of large format or very
• the EP 1170264 Bl teaches the production of translucent glass-ceramics with a comparatively high
• Keatite mixed crystal phase is in the cooling in the
• the high-quartz mixed crystal phase can be problematic on the one hand in terms of their acid resistance and on the other hand only by a very precise
• a certain structural sequence is formed, which contributes to the good mechanical properties of the glass-ceramic. If this sequence is interrupted or altered by reworking, such as cutting or sanding, weak spots may arise in these areas. So can
• the mechanical and chemical resistance of machined glass-ceramics to be significantly worse than the unprocessed.
• the inner glass ceramic structure is then open and partly provided with microcracks on the
• the invention is therefore based on the object, a
• the improved mechanical and chemical properties in particular a higher Shock resistance and improved acid resistance.
• a method is to be developed with which the product according to the invention can be produced.
• the glass ceramic comprehensive article may be translucent or preferably opaque.
• Processing steps of any kind for example by grinding or applying a coating or
• a precursor article made of glass to the glass-ceramic article comprising at least one first crystal phase comprises, converted or ceramized.
• a first crystal phase of a precursor article made of glass to the glass-ceramic article comprising at least one first crystal phase comprises, converted or ceramized.
• it will be a first crystal phase of a precursor article made of glass to the glass-ceramic article comprising at least one first crystal phase of a precursor article made of glass to the glass-ceramic article comprising at least one first crystal phase.
• Precursor article comprising at least this first crystal phase, in a second crystal phase of the
• Crystal phase content is less than 10 vol.%, Or a
• This phase transformation can consist of nucleation in a green glass and the subsequent crystallization and growth of crystallites. However, it may also mean the conversion of an already existing first crystal phase in a pre-ceramized precursor article into a different or even a second crystal phase.
• a transformation into a different or even a second crystal phase is understood to mean, in particular, a structural and compositional change as it is
• a glass-ceramic precursor article it may have been ceramified independently, in particular temporally independently, by the conversion according to the invention.
• the precursor article may therefore have been cooled to room temperature in the meantime.
• the invention also covers the case that a glass-ceramic precursor article directly in front of the
• the precursor article and the glass-ceramic-comprising article can also be created in a continuous process.
• a precursor article can be colored metal oxides
• the glass-ceramic-comprising article made from this precursor article is volume-dyed.
• the term "translucent" glass-ceramic article is understood to mean an article having a transmittance of 0.10 to 0.95 in the range of 400 to 1600 nm, whereas an article comprising "opaque" glass-ceramic exhibits virtually no transmission; it has a transmittance of 0 to 0.10.
• Wall thicknesses in the same way ie by means of the same Process parameters, was produced, quite translucent at a small thickness and may appear opaque at greater thickness, the degree of transmission and thus the terms "translucent” and "opaque” on a wall thickness of 4 mm to understand.
• the precursor article is heated to a maximum temperature during the process.
• Achievement of the maximum temperature is preferably greater than 10 K / min, and is preferably between 14 and 36 K / min.
• the heating rate is not limited by the process upwards, but depending on the technical possibilities, e.g. the efficiency of the furnace used.
• the maximum temperature After reaching the maximum temperature is followed by a very small retention time compared to the prior art, the maximum temperature of not more than two minutes.
• a holding time is substantially or completely omitted. This is advantageous because
• the inventive method is basically up
• the first mechanism involves the phase transformation starting at different locations on the precursor article at different times and at different rates.
• the phase transformation is generated
• Glass-ceramic object has only a small
• the glass-ceramic article further ceramics after reaching the maximum temperature.
• Microstructure can come. This allows individual phases to accumulate with different components and thus theirs
• Maximum temperature of the process and a rapid cooling freezes all phase conditions and prevents any form of further crystallization, material enrichment and structural type change, or at least reduced in terms of properties to an uncritical level.
• the inventors have surprisingly found that can be produced with relatively high heating rates and in particular very low holding times products with a novel structure, which are characterized by their high impact resistance and very good acid resistance. A detailed description of the advantages of the product according to the invention follows later.
• the homogeneity of crystallization depends not only on the size and wall thickness of the ceramic to be ceramized
• ceramizing precursor article should therefore be heated as evenly as possible in order to ensure a horizontally and preferably also laterally as uniformly as possible ceramization.
• the warm-up is uneven, there is a risk of deformation or warping of the article comprising glass-ceramic.
• One way to at least partially avoid these bends or distortions is to
• the articles comprising glass-ceramic can be produced individually in batch furnaces which have only a small furnace volume. Due to the low furnace volume, fast temperature control is possible. On the other hand, there are no chimney effects that can lead to temperature blur, for example, in a production in the roller furnace. However, a production in the roller furnace should not be presented as disadvantageous. Here only the effort to produce a uniform heating is greater. In this context, it is advisable, for example, to heat the ceramic article
• a heating of the top and bottom of the ceramic precursor article can be made.
• a particularly preferred embodiment of the invention therefore provides that the temperature gradient between the top and bottom of the precursor article is kept as low as possible.
• the temperature deviations between top and bottom should therefore preferably not more than
• Planarity deviations can be greatly reduced or even completely avoided.
• Precursor article preferably continuously and in particular in the critical period of
• the precursor article can thus be recognized and regulated by correction or adaptation of the furnace heating according to predetermined target values.
• Temperature control in the ceramic precursor article advantageously also a horizontal temperature control can be made.
• the heating of the furnace or the chamber in which the phase transformation is carried out regulated so that the temperature distribution across the width and / or the length of the converting
• the precursor article deviates at most +/- 5 K from a mean temperature in the converting precursor article.
• the vertical or horizontal temperature changes can be recorded, for example, by means of temperature sensors, which are in close proximity to the ceramizing
• Precursor object are arranged.
• these temperature sensors have a reaction time of less than ten seconds, preferably of a maximum of one second.
• the heating should preferably within 10 seconds, more preferably within one
• a particular advantage of the method according to the invention is the dimensional accuracy that exists between the precursor article and the glass-ceramic article. Apart from the volume change by the phase transformation, the precursor article hardly changes its shape during the conversion. This is particularly advantageous when shaped bodies, such as bowls for a wok, are ceramized. Particularly advantageous here already
• ceramified precursor article which is then subjected to a phase transformation according to the invention. Since the object already has at least one
• the Shape of the wok corresponds essentially, ie without
• a glass ceramic-comprising article according to the invention is produced by means of a method as described above.
• a glass ceramic comprehensive article is characterized
• the at least three different microstructures can be distinguished, for example, from one another by means of different ion contents in the transverse profile. If the ion gradients are measured perpendicular to the transition regions between the individual structures, characteristic differences for the individual microstructures result.
• the relative ion content gradients can be determined by means of
• Ions are preferably cations which are involved in the formation of the most important phases or main phases of the glass-ceramic article according to the invention. For example, if an LAS glass-ceramic is involved, ions showing intensity plateaus are, for example, Na, K, Li. and Mg cations Such single-ion intensity plateaus in various microstructure regions are not known in the prior art.
• transitions between regions with different structures typically form the morphology of the
• Interfaces i. its contours or edges to the environment according to, the areas of different structures from the edge to the interior of the glass-ceramic comprehensive article
• the microstructures can also be determined on the basis of the ratio of
• An outer region encompassing the interface with the surrounding area of the glass-ceramic article comprises
• a largely amorphous first microstructure Under a largely amorphous surface layer or a largely amorphous first structure is a near-surface
• Structural area to be understood which has a thickness of 30 to 6000 nm and less than 10 vol.%
• this microstructure region preferably has no crystallites of the main crystal phases of the glass-ceramic article. In any case, however, include max. 10 vol .-% of the crystallites contained in the amorphous edge region or the main crystal phase.
• a second, adjacent to the first region, comprises a second structure having a crystallite content between 10 and 80 vol .-%.
• a third, adjacent to the second region comprises a third structure having a crystallite content of over 80% by volume. This structure forms the interior of the
• An especially preferred embodiment of the article comprising glass-ceramic has an acid resistance according to DIN 12 116 of class 1 or 2.
• Such a glass-ceramic article can therefore be used advantageously in production processes, for example as a laboratory device or for interior lining of furnaces or the like, in which aggressive substances be used.
• a glass ceramic comprising 200 x 200 x 4 mm article has fracture drop heights greater than 15 cm, preferably greater than 20 cm, and most preferably less than 25 cm (5% Weibull distribution fractile).
• the impact resistance is one
• the test is based on the ball drop test according to DIN 52306.
• the chemical resistance can also be demonstrated by the S test by exposing a glass ceramic article according to the invention to an attack of concentrated sulfuric acid at a temperature of 370 ° C. for 30 minutes. In a subsequent ball drop test as described above, the items still show
• This area with mixed crystals in deep-quartz structure has a coefficient of thermal expansion greater than 13 ⁇ 10 -6 K -1 and is thus significantly higher than the coefficient of thermal expansion in the interior of the
• the article according to the invention comprises, for example, the following mechanical or chemical
• the high impact and temperature differential strengths enable the use of glass ceramics according to the invention of comprehensive articles in areas in which there are strong temperature differences over short distances. It may be, for example, cooktops, oven panes, but also white goods or glass ceramic cooking vessels.
• the use as a cooking vessel, for example, makes sense only by the impact resistance of the glass ceramic comprehensive objects. Particularly advantageous in this context is that in the visual
• Wavelength range opaque inventive objects in the infrared wavelength range may have a transparency of> 70%.
• thermal stability also leads to the article according to the invention almost no particles and
• Substances / components of the composition delivered can be used in the pharmaceutical industry as containers or plant components, in thermal systems z. B. as
• Furnace linings of tempering ovens and chemical or physical coating plants in the solar industry as well as high performance ceramics are used.
• the latter is primarily favored by the fact that the required geometries are easy to produce and provided with smooth surfaces.
• façade panels which can additionally be provided with functional surfaces, for example for nitrogen oxide bonding
• Ceramic materials is that they have no
• heating elements in particular as a cooking or roasting surface and as white goods
• thermo-mechanical stress for applications with thermo-mechanical stress, for example in night vision devices
• a glass ceramic comprising article may have the following composition:
• a glass-ceramic-comprising article which corresponds to one of the abovementioned compositions may have a first largely amorphous microstructure which is depleted of Li and Mg ions relative to the second and third microstructures and enriched in Na and K ions.
• the described ion content profiles in the various structures may have a first largely amorphous microstructure which is depleted of Li and Mg ions relative to the second and third microstructures and enriched in Na and K ions.
• a second microstructure which adjoins the first largely amorphous microstructure, may advantageously be enriched in Li and Mg ions relative to the first microstructure.
• the cations Na and K are relative to the first structure
• Li and Mg ions are enriched relative to the first two structures.
• Na and K ions are depleted relative to the other two structures.
• the two first structural regions preferably have a thickness or thickness perpendicular to the transition regions of the microstructure of not more than 10 ⁇ m and preferably of not more than 5 ⁇ m, it being possible to differentiate the microstructure on the basis of the ion gradient profiles. According to a particularly preferred embodiment of
• the invention comprises at least the third structure of
• Glass ceramic comprehensive article a main crystal phase of keatite mixed crystals and a second crystal phase of high quartz mixed crystals, wherein the ratio between the high quartz mixed crystal phase and the keatite mixed crystal phase to the edge of the glass-ceramic comprising article increases continuously or in stages , Since the high-quartz mixed-crystal phase has a lower coefficient of thermal expansion than the keatite mixed-crystal phase, stresses arise which increase comparatively continuously from the inside to the outside.
• Glass ceramic comprising minority crystal phases such as gahnite mixed crystals or
• Gahnit doping can be equated, advantageously, the acid resistance of the glass ceramic comprehensive
• a particularly preferred glass ceramic comprising article comprises a marginal portion of the first largely amorphous structure which is enriched in gahnite mixed crystals.
• a particularly preferred glass ceramic comprising article comprises a marginal portion of the first largely amorphous structure which is enriched in gahnite mixed crystals.
• the invention is in the marginal region of the first largely amorphous structure at least one Gahnit doping before.
• Fig. 2a the different structural areas of a
• FIG. 3 shows thin-film X-ray diffraction measurements (DS-XRD) from different depth ranges (FIGS. 3a-3c) of an article comprising glass-ceramic material according to the invention
• Fig. 1 is a temperature-time diagram of a
• Green glass precursor article can be produced.
• the time is shown on the x-axis and the temperature on the y-axis.
• the method can also be used with a
• pre-ceramized precursor which is temporally and optionally spatially separate from the preparation of the
• a green glass precursor article having a lithium aluminum silicate (LAS) composition is first converted to a precursor article having a high quartz mixed crystal phase and then to a glass ceramic article comprising at least one keatite mixed crystal phase.
• LAS lithium aluminum silicate
• coloring oxides may be included.
• the precursor article is heated from room temperature to about 660 ° C. over 11 minutes at a heating rate of 58 K / min or even up to 150 K / min.
• the heating rate in this first area of heating can generally be chosen as high as possible, since the viscosity of the precursor article is so low that hardly any internal stresses occur.
• the heating rate is then slowly lowered to zero, so that either one
• volume crystallization of the high quartz mixed crystal phase for example.
• a homogenization of the temperature of the article to be ceramized takes place.
• this homogenization phase is only optional, ie it is not necessarily process-specific and therefore not absolutely necessary. The holding time during this
• Process step is about 30 minutes.
• volume crystallization is not critical.
• the ceramizing precursor article is heated to a heating rate of about 30 K / min
• the heating rate in this process period should generally be greater than 10 K / min and more preferably between 14 and 36 K / min, the upper limit of the heating rate being due to the technical possibilities.
• Prehistoric article is heated to a maximum temperature, wherein at least 80% of the volume change
• Precursor during the transformation of the high quartz Mixed crystal phase in the keatite mixed crystal phase of the glass ceramic comprehensive article undergoes within a one to six minutes, preferably completed within a one to four minutes and more preferably within a one to two minutes time window and thereby a heating rate to achieve the
• Maximum temperature greater than 10 K / min, preferably between 14 and 36 K / min is driven. Without observing a hold time at the maximum temperature, the precursor article then becomes about 400 ° C., with an average cooling rate of about 350 K / min
• the precursor article should be heated as evenly as possible, at least during the exothermic phase transition phase.
• the should should be heated as evenly as possible, at least during the exothermic phase transition phase.
• the desired homogeneous heating of the ceramizing precursor article is preferably monitored by means of sensors and the oven temperature is regulated as a function of the measured values.
• an effective control of the oven temperature requires, because of the very low conversion times of a few minutes, that the regulation takes place within a very short time. Therefore, the temperature sensors or sensors preferably have a reaction time of less than ten seconds, more preferably of a maximum of one second.
• the control of the heating is preferably carried out within 10 seconds and
• Figs. 2a and 2b show an SEM image of a
• the glass ceramic comprehensive article and the associated ion content gradients which were determined by means of SIMS measurements.
• the SIMS measurements are represented in a coordinate system showing the depth on the x-axis from the edge of the glass-ceramic object to the center and the intensity in logarithmic representation on the y-axis.
• FIG. 2 a There are three different microstructure regions 1, 2, 3 in the profile section as well as the associated ionic gradients of the upper side (FIG. 2 a) and the underside (FIG. 2 b) of an article comprising glass-ceramics.
• FIG. 2b serves for the similarity to substantiate the structural formations of the top and bottom of a glass-ceramic comprehensive article.
• a first largely amorphous microstructure region 1 is located at the edge of the glass-ceramic article.
• This area 1 can be up to six microns thick. In the example shown in Fig. 2a, it has a thickness of about 570 nm.
• This microstructure region 1 is characterized by a glassy, that is essentially amorphous, matrix
• characterized maximally 10 vol .-% comprises crystallites.
• Na-4 and K-ions 5 are enriched in this first largely amorphous region 1 relative to the two other regions 2, 3, while Li-6 and Mg-ions 7
• Zn ions 12 are in particular in
• intensity plateau 9 is not understood as meaning a constant ion content profile in the narrower sense; but it is primarily the contrast between higher rising or falling levels, for example in the transition areas between the individual structures and to be emphasized only slowly or slightly changing levels of individual ions within the microstructure.
• the region 2 which adjoins the interior of the first largely amorphous microstructure region 1 is characterized by a crystallite content of 10 to 80% by volume.
• crystallite sizes increase from outside to inside.
• This second microstructure region 2 shows a relative accumulation of Li-6, Mg-7 and Zn ions 12 in comparison to the first largely amorphous microstructure region 1.
• the Na-4 and K-ions 5 are largely amorphous compared to the first
• the second microstructure region 2 in this specific case comprises about one micrometer, but may generally be in the range of 0.03 to 5.00 microns.
• the third microstructure area 3 is characterized by a
• Crystallite content of greater than 80% by volume.
• the Crystallites are significantly larger at 0.05-100 ⁇ m than in the two other microstructure areas 1, 2.
• This third microstructure area 3 forms the interior of the glass-ceramic
• the grading curves show for this third microstructure region 3 a relative accumulation of Li-6, Mg-7 and Zn ions 12 as well as a relative depletion of Na-4 and K-ions 5 in comparison to the other two microstructure regions 1, 2 or structures.
• the Si-ion content 8 is constant substantially from the first 1 to the third microstructure 3, except for a very slight trend towards decreasing relative contents. he hardly shows structure-specific changes.
• the most conspicuous secondary crystal phases are needle-shaped or rod-shaped gahnite mixed crystals 10 and cubic or cubic zirconium titanate mixed crystals 11 in all three microstructure regions 1, 2, 3.
• phases such as rutile mixed crystals as minority constituents
• the Gahnit mixed crystals 10 seem to dominate the crystal phase in the first largely amorphous microstructure region 1.
• the Zn-ion content profile 12 shows an enrichment, in particular in the marginal or near-surface region of the first microstructure region 1. It can be assumed that the Zn content of the
• Glass ceramic essentially reflects the Zn content of Gahnit mixed crystals 10.
• the inventors suggest that the relative accumulation of gahnite mixed crystals in the marginal region can at least partially explain the improved chemical resistance of the glass-ceramic article according to the invention, since gahnite has good acid resistance.
• gahnite has good acid resistance.
• FIG. 3 shows DS-XRD measurements for the depths 0 to 2, 5 ⁇ m (FIG. 3a), 0 to 5 ⁇ m (FIG. 3b) and 0 to 10 ⁇ m (FIG. 3c), measured from the surface, shown.
• the diffraction angle is plotted on the x-axis of these figures and the intensity on the y-axis.
• FIGS. 3a-3c indicate the presence of Si-rich high-quartz mixed crystals 13 and keatite mixed crystals 14 as main crystal phases and of zirconium titanate mixed crystals 15 as secondary constituent.
• the method guarantees certain
• the glass-ceramic has a surface thickness range due to gradients of K, Na, Zn and Li ions
• a glass-ceramic comprises a comprehensive article having a LAS composition associated with the
• the interior of the glass-ceramic comprising article is dominated by a keatite solid solution phase 14 with a thermal expansion coefficient of about 1 x 10 "6 K '1. With increasing relative high quartz solid solution content 13 to the outside, this thermal increases
• Microstructure 1 however, has a thermal
• An article with a wall thickness of 4 mm comprising a glass ceramic produced by the process according to the invention has, for example, the following mechanical and chemical properties
• a glass ceramic comprising the present invention dispenses little to no particles.
• a delivery of other material components such as alkali or alkaline earth metal ions, etc. is only under extreme conditions, highest temperatures and extremely long operating times for sulfur-containing materials
• FIG. 4 shows the relative change in length of articles comprising glass-ceramic as a function of the temperature for a temperature range between zero and about 950 ° C. It becomes clear that a glass ceramic is more comprehensive
• the object is maximally extended by 0.16% when heated from zero to about 950 ° C.
• For this temperature range is the maximum average thermal

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• Crystallography & Structural Chemistry (AREA)
• Dispersion Chemistry (AREA)
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• 2010
  • 2010-01-28 DE DE102010006232.4A patent/DE102010006232B4/de active Active
  • 2010-07-13 WO PCT/EP2010/004250 patent/WO2011009544A1/de not_active Ceased
  • 2010-07-13 JP JP2012520928A patent/JP5892932B2/ja not_active Expired - Fee Related
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  • 2010-07-13 EP EP10734044.0A patent/EP2456729B1/de active Active
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